Functionalized polyphenylene ethers and blends with polyamides

ABSTRACT

Functionalized polyphenylene ether compositions are provided which are particularly useful for effecting compatibility for a blend of polyphenylene ether resin and a polyamide resin. The functionalized-polyphenylene ether is the reaction product of a polyphenylene ether polymer and a compound having the general formula (i)--Z--(ii), wherein group (i) is a polyphenylene ether-philic moiety such as acyl chloride, group (ii) is a polyamide-philic moiety such as dicarboxylic acid anhydride, and Z is a divalent hydrocarbon radical providing a covalent linkage between groups (i) and (ii). An example of the compound having general formula (i)--Z--(ii) is trimellitic anhydride acid chloride.

This is a divisional of application Ser. No. 780,151 filed Sept. 26,1985 now Pat. No. 4,824,915.

FIELD OF THE INVENTION

The present invention relates to a novel class of functionalizedpolyphenylene ether compounds which are a reaction product of apolyphenylene ether polymer and another compound which contains in itsmolecule both (i) at least one "acyl" functional group and (ii) at leastone group capable of reacting or associating with a polyamide resin. Afurther discovery concerns the utilization of thisfunctionalized-polyphenylene ether to provide compatible thermoplasticblends with polyamide resins. The functionalized-polyphenylene ether maybe combined with the polyamide resin to provide the thermoplastic blend.Additionally, the functionalized polyphenylene ether can be used tocompatibilize a thermoplastic blend of polyamide and conventionalpolyphenylene ether.

The compatible polyphenylene ether-polyamide compositions of the presentinvention exhibit improved chemical resistance, processability,elongation properties and impact strength.

BACKGROUND OF THE INVENTION

The polyphenylene ether resins are characterized by a unique combinationof chemical, physical and electrical properties over a temperature rangeof more than 650° F., extending from a brittle point of about -275° F.to a heat distortion temperature of about 375° F. This combination ofproperties renders the polyphenylene ethers suitable for a broad rangeof applications. However, in spite of the aforementioned beneficialproperties, the usefulness of the polyphenylene ether resins is limitedin some applications as a consequence of processability, impactresistance and chemical resistance.

Finholt (U.S. Pat. No. 3,379,792) discloses polymer blends wherein theprocessability of polyphenylene ether resins may be improved by blendingwith from 0.1 to 25% by weight of a polyamide. However, the advantagesof the Finholt invention are limited by the fact that when theconcentration of the polyamide exceeds 20% by weight, appreciable lossesin other physical properties result. Specifically, there is no, or atbest poor, compatibility between the polyphenylene ether and thepolyamide such that phase separation of the resins occurs on molding orthe molded article is inferior in mechanical properties.

Ueno et al. (U.S. Pat. No. 4,315,086) discloses polyphenylene etherblends having improved chemical resistance without a loss of othermechanical properties by blending therewith a polyamide and a specificcompound selected from the group consisting essentially of A) liquiddiene polymers, B) epoxy compounds and C) compounds having in themolecule both of i) an ethylenic carbon-carbon double bond orcarbon-carbon triple bond and ii) a carboxylic acid, acid anhydride,acid amide, imide, carboxylic acid ester, amino or hydroxy group.

Finally, Kasahara et al (EP46040) discloses the use of a copolymercomprising units of a vinyl aromatic compound and either an alpha,beta-unsaturated dicarboxylic acid anhydride or an imide compoundthereof as a modifier to an impact resistant polyphenyleneether-polyamide blend for improved heat resistance and oil resistance.

The present applicants have disclosed novel polyphenyleneether-polyamide blends having improved impact strength, elongation,chemical resistance, processability and/or heat resistance as well asreduced water absorption as compared to unmodified polyphenyleneether-polyamide compositions.

Specifically, applicants have discovered novel resin compositions havingthe aforementioned properties comprising a blend of a polyamide with orwithout a conventional polyphenylene ether and a property improvingamount of the effective functionalized-polyphenylene ethercompatibilizer described in detail below.

The functionalized-polyphenylene ether is a polyphenylene ether polymerwhich has been reacted with another compound which contains in itsmolecule both of two groups (i) and (ii) which are described in detailbelow. The molecule containing both groups (i) and (ii) is nominally an"acyl-functional"moiety within the broad definition of such materialsbelow. The group (ii) portion of the molecule is considered to be apolyamide-philic moeity.

Accordingly, the functionalized-polyphenylene ether compatibilizingcompound is provided by the reaction of a polyphenylene ether polymerand a compound containing the requisite, aforementioned groups (i) and(ii). The resultant product is the reaction residue of the polyphenyleneether polymer and the group (i), (ii) molecule.

An example of a molecule containing the requisite group (i) and group(ii) moieties is trimellitic anhydride acid chloride.

It has been discovered, for example, that polyphenylene ether polymermay be reacted with trimellitic anhydride acid chloride (TAAC) and thereaction product (PPE-TAAC) functions very effectively as acompatibilizer for polyphenylene ether-polyamide blends. With properimpact modification, the resultant blends exhibit very attractivephysical properties such as high heat distortion temperature (HDT), goodimpact strength and mechanical properties, low shrinkage, andoutstanding chemical resistance and hydrolytic stability for manyend-use applications.

It also has been discovered that PPE-TAAC is superior to maleicanhydride as a compatibilizer for polyphenylene ether/polyamide (PPE/PA)blends in many respects.

For example, PPE-TAAC compatibilizer offers better color stability.Significant discoloration after extrusion was observed for PPE/Nylon(6/6) blends which were compatibilized with maleic anhydride in themanner taught by UENO, et al. Such discoloration was not evident inPPE/PPE-TAAC/Nylon 6/6 blends of the present invention.

The functionalized-polyphenylene ether compatibilizer also offersimproved dimensional stability. Higher mold shrinkage was observed inprior art PPE/Nylon (6/6)/maleic anhydride blends in comparison withPPE/PPE-TAAC/Nylon (6/6) blends of the present invention havingcomparable physical properties.

The functionalized-polyphenylene ether compatibilizer also offers highermatrix ductility. Impact modified PPE/Nylon (6/6)/maleic anhydrideblends from the prior art exhibited significantly lower Izod impactstrength and less ductile failure behavior in a falling dart test thancorresponding PPE/PPE-TAAC/Nylon (6/6) blends of the present invention.The mode of ductile failure can be an extremely important considerationwhen choosing a thermoplastic for various end-use applications.

The functionalized-polyphenylene ether compatibilizer provides betterphase dispersion and interfacial adhesion. PPE/Nylon (6/6)/maleicanhydride blends were judged from morphology and solubility test resultsto have much inferior phase dispersion and interfacial adhesion comparedto PPE/PPE-TAAC/Nylon (6/6) blends of the present invention.

SUMMARY OF THE INVENTION

The novel functionalized-polyphenylene ether, which may be incorporatedin novel, compatible blends of polyphenylene ether and polyamide, is thereaction product of

(a) a polyphenylene ether polymer, and

(b) a compound of the general formula

    (i)--z--(ii)

which is a compound that contains in its molecule both group (i) whichis at least one group having the formula ##STR1## where X is F, Cl, Br,I, OH, OR, or ##STR2## where R is H or an alkyl or aryl radical andgroup (ii) which is at least one carboxylic acid, acid anhydride, acidamide, imido, carboxylic acid ester, amino or hydroxyl group; whereingroups (i) and (ii) are covalently bonded through linkage Z, where Z isa divalent hydrocarbon radical. Z may be either a divalent alkyl or arylradical linking groups (i) and (ii), and would be comprised of at leastone and typically one to six carbon atoms.

In the compound having the formula (i)--z--(ii), groups (i) and (ii)will not both be carboxylic acid groups at the same time. Thus, althoughgroup (i) may be a carboxylic acid group (--COOH), in such case group(ii) would not contain one or more carboxylic acid groups. Rather, inthis instance, group (ii) might preferably be an anhydride group. Theconverse is also true, if group (ii) of the compound contains one ormore carboxylic acid groups, then group (i) would not be --COOH. In thiscase, group (i) would preferably be an acyl chloride group or similarmoiety.

The invention also encompasses combining this functionalizedpolyphenylene ether with a polyamide. Such combination may be a physicaladmixture by conventional means, a chemical reaction product of thevarious components, and blends and reaction products of variouscombinations of the requisite materials which may be later combined intoa compatible product. The expressions "polyphenylene ether-polyamideblend" and "PPE-PA" are intended to encompass each of thesepossibilities.

The compatibilizing compound provided by the present invention canprovide compatible blends of polyphenylene ether and polyamide in anyproportion. Typically, however, the polyphenylene ether will be presentin an amount of 5 to 95 weight percent and the polyamide will be presentat 95 to 5 weight percent, based upon the weights of both resinstogether.

A preferred composition might comprise 25 to 75 weight percentpolyphenylene ether and 75 to 25 weight percent polyamide.

The compatibilizing compound will be present in an amount at leastsufficient to effect compatibility of the resinous components and isintended to encompass adequate dispersion of the two resins in a mannerwhich provides useful thermoplastic compositions, as well as usefulnon-delaminatning products.

Typically, at least about 1 part by weight of the compatibilizingcomponent will be necessary per 100 parts of resinous components.Preferred formulations may contain, approximately 10 to 30 parts byweight of compatibilizing component per 100 parts resin.

Thus a typical embodiment comprises an admixture of polyphenylene ether,polyamide and a functionalized polyphenylene ether compatibilizing agentsuch as polyphenylene ether reacted with trimellitic anhydride acidchloride (PPE-TAAC).

Alternatively, the compatibilizing agent can first be precompounded orpre-reacted with either of the two resinous materials.

Furthermore, the functionalized polyphenylene ether such aspolyphenylene ether-trimellitic anhydride acid chloride reaction product(PPE-TAAC) can replace all or some of the conventional polyphenyleneether in a polyphenylene ether/polyamide product.

Preferred polyphenylene ethers are homopolymers or copolymers havingunits with the repeating structural formula: ##STR3## wherein the oxygenether atom of one unit is connected to the benzene nucleus of the nextjoining unit, and n is a positive integer of at least 50, and each Q is,independently, a monovalent substituent selected from a group consistingof hydrogen, halogen, hydrocarbon and hydrocarbonoxy groups free of atertiary alpha-carbon atom, and halohydrocarbon and halohydrocarbonoxygroups free of a tertiary alpha-carbon and having at least 2 carbonatoms between the halogen atom and the phenyl nucleus.

A particularly preferred polyphenylene ether ispoly(2,6-dimethyl-1,4-phenylene) ether.

Compatible compositions are intended to include any of the well knownpolyamides or nylons such as polyamide 6; polyamide 6/6; polyamide 4/6;polyamide 12; and polyamide 6/10, combinations of these whereappropriate, as well as high impact, super toughened polyamides.Polyamide 6/6 or polyamide 6 is preferred.

Optionally, the compositions of the present invention may furthercomprise polymeric impact modifiers, inorganic reinforcing additives orother polymers including alkenyl aromatic polymers such as the styrenicpolymers.

Improved polyphenylene ether-polyamide compositions may be made by meltblending the above-mentioned ingredients. Alternatively, to achieveoptimum property improvements it may be preferred to precompound theproperty improving compatibilizing agent, together with either one ofthe polymer resins.

Although the exact physical configuration of the compositions of thepresent invention is not known, it is generally believed that thecompositions comprise a dispersion of one polymer in the other. A likelyconfiguration is wherein the polyphenylene ether is dispersed in apolyamide matrix, however, the inverse may also be possible,particularly where the polyamide is present in only a minor amount. Itwill be recognized that good dispersion of one polymer in the other willordinarily afford a useful, compatible thermoplastic product. Thefunctionalized-polyphenylene ether compatibilizing compound of thepresent invention has been found to achieve such dispersion. Applicantsalso contemplate that there may be present in the products producedhereby some graft polyphenylene ether-polyamide products. Thus, all suchdispersions as well as graft, partially grafted and non-grafted productsare within the full intended scope of the invention.

DETAILED DESCRIPTION OF THE INVENTION

The polyphenylene ethers suitable for use in the practice of the presentinvention are well known in the art and may be prepared by any of anumber of catalytic and non-catalytic processes from correspondingphenols or reactive derivatives thereof. Examples of polyphenyleneethers and methods for their production are disclosed in U.S. Pat. Nos.3,306,874; 3,306,875; 3,257,357; 3,257,358; 3,337,501 and 3,787,361, allincorporated herein by reference. For brevity, the term "polyphenyleneether" as used throughout this specification and the appended claimswill include not only unsubstituted polyphenylene ether (made fromphenol) but also polyphenylene ethers with various substituents. Theterm also includes polyphenylene ether copolymers; as well as graft andblock copolymers of alkenyl aromatic compounds, especially vinylaromatic compounds, as disclosed below, and a polyphenylene ether.

Suitable phenol compounds for the preparation of the polyphenyleneethers may be represented by the general formula: ##STR4## wherein eachQ is a monovalent substituent individually selected from the groupconsisting of hydrogen, halogen, aliphatic and aromatic hydrocarbon andhydrocarbonoxy radicals free of a tertiary alpha-carbon atom andhalohydrocarbon and halohydrocarbonoxy radicals free of a tertiaryalpha-carbon atom and having at least two carbon atoms between thehalogen atom and the phenyl nucleus, and wherein at least one Q ishydrogen.

As specific examples of the phenol compound represented by the aboveformula, there may be given phenol; o-, m- and p- cresols; 2,6-, 2,5-,2,4- and 3,5-dimethylphenols; 2-methyl-6-phenyl-phenol;2,6-diphenylphenol; 2,6-diethylphenol; 2-methy-6-ethyl-phenol; and2,3,5-, 2,3,6- and 2,4,6-trimethylphenols. Two or more phenol compoundsmay be used in combination should copolymers be desired. Additionally,copolyphenylene ethers may also be prepared from a phenol compound ofthe above general formula with a phenol compound not represented by theabove general formula including, for example, a dihydric phenol such asbisphenol-A, tetrabromobisphenol-A, resorcinol or hydroquinone.

Illustrative of suitable polyphenylene ethers there may be given forexample, poly(2,6 dimethyl-1,4-phenylene)ether;poly(2-methyl-1,4-phenylene) ether, poly(3-methyl-1,4-phenylene)ether;poly(2,6-diethyl-1,4-phenylene)ether;poly(2-methyl-6-allyl-1,4-phenylene)ether;poly(2,6-dichloromethyl-1,4-phenylene)ether;poly2,3,6-trimethyl-1,4-phenylene)ether;poly(2,3,5,6-tetramethylphenylene)ether;poly(2,6-dichloro-1,4-phenylene)ether;poly(2,6-diphenyl-1,4-phenylene)ether;poly(2,5-dimethyl-1,4-phenylene)ether and the like. Further, asmentioned above, copolymers of the phenol compounds may also be used.

Preferred polyphenylene ethers will have the formula: ##STR5## where Qis as defined above and n is at least 50, preferably from about 50 toabout 200. Examples of polyphenylene ethers corresponding to the aboveformula can be found in the above referenced patents and include, amongothers: poly(2,6-dilauryl-1,4-phenylene)ether;poly(2,6-diphenyl-1,4-phenylene)-ether;poly(2,6-dimethyoxy-1,4-phenylene)ether;poly(2,6-diethyoxy-1,4-phenylene)ether;poly(2-methoxy-6-ethyoxy-phenylene)ether;poly(2-ethyl-6-tearyloxy-1,4-phenylene)ether;poly(2,6-dichloro-1,4-phenylene)ether;poly(2-methyl-6-phenyl-1,4-phenylene)etherpoly(2,6-dibenzyl-1,4-phenylene) ether;poly(2-ethoxy-1,4-phenylene)ether; poly(2-chloro-1,4-phenylene)ether;poly(2,6-dibromo-1,4-phenylene)-ether; and the like.

For the purpose of the present invention, an especially preferred familyof polyphenylene ethers include those having a C₁ to C₄ alkylsubstitution in the two positions ortho to the oxygen ether atom.Illustrative members of this class are:poly(2,6-dimethyl-1,4-phenylene)ether:poly(2,6-diethyl-1,4-phenylene)ether;poly(2-methyl-6-ethyl-1,4-phenylene)ether;poly(2,6-dipropyl-1,4-phenylene)ether;poly(2-ethyl-6-propyl-1,4-phenylene)ether; and the like; most preferablypoly(2,6-dimethyl-1,4-phenylene)ether.

One method for the production of the above polyphenylene ethers is bythe oxidation of a phenol compound by oxygen or an oxygen-containing gasin the presence of a catalyst for oxidative coupling. There is noparticular limitation as to the choice of catalysts and any catalystsfor oxidation polymerization can be employed. As typical examples of thecatalyst, there may be given a catalyst comprising a cuprous salt and atertiary amine and/or secondary amine, such as cuprouschloride-trimethylamine and dibutylamine, cuprous acetate-triethylamineor cuprous chloride-pyridine; a catalyst comprising a cupric salt, atertiary amine, and an alkali metal hydroxide, such a cupricchloride-pyridine-potassium hydroxide; a catalyst comprising a manganesesalt and a primary amine, such as manganese choride-ethanolamine ormanganese acetate-ethylenediamine; a catalyst comprising a manganesesalt and an alcholate or phenolate, such as manganese chloride-sodiummethlate or manganese chloride-sodium phenolate; and a catalystcomprising a cobalt salt and a tertiary amine.

Polyamides suitable for the preparation of compatible compositions maybe obtained by polymerizing a monoamino-monocarboxylic acid or a lactamthereof having at least 2 carbon atoms between the amino and carboxylicacid group; or by polymerizing substantially equimolar proportions of adiamine which contains at least 2 carbon atoms between the amino groupsand dicarboxylic acid; or by polymerizing a monoaminocarboxylic acid ora lactam thereof as defined above together with substantiallyequimolecular proportions of a diamine and a dicarboxylic acid. Thedicarboxylic acid may be used in the form of a functional derivativethereof, for example an ester or acid chloride.

The term "substantially equimolecular" proportions (of the diamine andof the dicarboxylic acid) is intended to encompass both strictequimolecular proportions and slight departures therefrom which areinvolved in conventional techniques for stabilizing the viscosity of theresultant polyamides.

Examples of the aforementioned monoamino-monocarboxylic acids or lactamsthereof which are useful in preparing the polyamides include thosecompounds containing from 2 to 16 carbon atoms between the amino andcarboxylic acid groups, said carbon atoms forming a ring with the--CO--NH-- group in the case of a lactam. As particular examples ofaminocarboxylic acids and lactams there may be mentionedgamma-aminocaproic acid, butyrolactam, pivalolactam, caprolactam,capryllactam, enantholactam, undecanolactam, dodecanolactam and 3- and4-aminobenzoic acids.

Examples of diamines suitable for preparing the polyamides includediamines of the general formula

    H.sub.2 N(CH.sub.2).sub.n NH.sub.2

wherein n is an integer of from 2 to 16, such as trimethylenediamine,tetramethylenediamine, pentamethylenediamine, octamethylenediamine andespecially hexamethylenediamine.

The dicarboxylic acids may be aromatic, for example isophthalic andterephthalic acids. Preferred dicarboxylic acids are of the formula

    HOOC--Y--COOH

wherein Y represents a divalent aliphatic group containing at least 2carbon atoms, and examples of such acids are sebacic acid,octadecanedoic acid, suberic acid, glutaric acid, pimelic acid andadipic acid.

Typical examples of the polyamides or nylons, as these are often called,include for example polyamides 6, 6/6, 11, 12, 6/3, 6/4, 6/10 and 6/12as well as polyamides resulting from terephthalic acid and trimethylhexamethylene diamide, polyamides resulting from solipic acid and metaxylylenediamines, polyamides resulting from adipic acid, azelaic acidand 2,2-bis-(p-aminocyclohexyl) propane and polyamides resulting fromterephthalic acid and 4,4'-diamino-dicyclohexylmethane. Preferredpolyamides are the polyamides 6, 6/6, 4/6, 11 and 12, most preferablypolyamide 6/6 or polyamide 6.

The blending ratio of polyphenylene ether to polyamide is 5 to 95% byweight preferably 25 to 75% by weight of the former to 95 to 5% byweight, preferably 75 to 25% by weight of the latter. When the polyamideis less than 5 weight percent, its effect to improve solvent resistanceis small, and when it exceeds 95 weight percent, thermal properties suchas heat distortion temperature tend to become poor.

Compatibility between the polyphenylene ether resin and the polyamideresin is believed to be achieved when the functionalized-polyphenyleneether compatibilizing agent is chemically or physically associated withthe polyphenylene and/or polyamide resins.

For example, a linear polyphenylene ether having an end group of formulaI: ##STR6## may be reacted in the presence of heat and solvent with anacyl compound having the general formula (i) --Z--(ii) such astrimellitic anhydride acid chloride of formula II: ##STR7## to provide aPPE-TAAC functionalized-polyphenylene ether compatibilizing agent offormula III, which may be appropriately purified as by precipitation inmethanol or acetone, and may thereafter desirably be filtered and dried:

It is evident in this example that the polyphenylene ether polymer hasreacted with the group (i) portion of the trimellitic anhydride acidchloride ##STR8## and the residue thereof is ##STR9##

The anhydride portion of this compatibilization agent ispolyamide-philic and is believed to be primarily responsible for thechemical or physical association of the agent with the polyamide resin.

Of course it is contemplated that the compatibilization agent can begeneralized to encompass a number of other effective agents which wouldact similarly to the preferred PPE-TAAC agents discussed above.

The compounds having formula (i)--Z--(ii) are in effectcompatibilization precursors inasmuch as they are reacted with apolyphenylene ether polymer to provide a functionalized-polyphenyleneether. This functionalized-polyphenylene ether effects compatibilitywith polyamides or with polyphenylene ether/polyamide compositions.

For example, the group (i) portion of the compatibilizing moleculeassociated or bonded to the PPE resin chain has been generalized as anacyl-functional group depicted by formula IV: ##STR10## where x is F,CL, Br, I, OH, OR or ##STR11## etc. and where R is H or an aliphatic oraromatic radical having less than about 10 carbon atoms. Thepolyphenylene ether-philic moiety of formula IV is covalently bonded toa polyamide-philic group which is primarily responsible for associatingor bonding with the polyamide portion of the thermoplastic composition.In a preferred embodiment such as TAAC discussed above, this group is ananhydride group.

Examples of suitable materials of general formula (i)--Z--(ii) andfalling within the scope of the invention include but are not limited tothe following compatiblizer precursors:

chloroethyanoylsuccinic anhydride ##STR12## trimellitic anhydride acidchloride ##STR13## chloroformylsuccinic anhydride ##STR14##1-acetoxyacetyl-3,4-dibenzoic acid anhydride ##STR15##

Of course, compatibilizer precursors effective in this invention are notlimited to the preferred anhydrides mentioned above. It is well knownthat polyamides will react or associate with a very large number ofmolecules containing groups chosen from among carboxylic acid (includingmono- and poly- acids), acid anhydride, acid amide, imido carboxylicacid ester, amino or hydroxyl groups. In this regard, reference is madeto the UENO patent discussed above.

Thus it is contemplated that the acid chloride of terephthalic acid canalso be utilized to provide the functionalized polyphenylene ether ofthe present invention.

The amount of the compound of formula (i)--Z--(ii) to be used tofunctionalize the polyphenylene ether polymer is that amount whichmanifests property improvement, especially improved compatibility aswell as improved processability, impact strength and/or elongation, inthe polyphenylene ether-polyamide compositions. In general, the amountof compatibilizer precursor of formula (i)--Z--(ii) used to react withpolyphenylene ether will be up to about 6%, preferably from about 0.05to about 4% by weight based on the polyphenylene ether. The specificamount of the compatibilizer to be used to achieve optimum results for agiven composition is dependent, in part, on the specific compatibilizerprecursor, the specific polyphenylene ether to be reacted, the specificpolyphenylene ether and polyamide to be compatibilized and the weightratio of said polymers and the processing conditions. A variety ofsuitable combinations can be achieved without undue experimentation.

In addition to the improved processability, impact strength andelongation, many of the compositions prepared in accordance with thepresent invention manifest improvements in other physical properties andcharacteristics including for example, reduced water absorption.

The above-mentioned property improving compatibilizer compound may beused alone or in combination with a primary or secondary amine. Thepresence of the amine may enhance the improvement of certain physicalproperties when used in combination with various compatibilizers.Suitable amines include those primary and secondary amines having from 1to about 20, preferably from 1 to about 10 carbon atoms. Examples ofsaid suitable amines are, methyl ethylamine, diethylamine, butylamine,dibutylamine, analine, n-octadecylamine and the like. The amount of theprimary or secondary amine to be used is generally up to about 3% byweight, preferably up to about 1% by weight.

In the practice of the present invention, it may be further desirable toadd rubbery high-molecular weight polymers to further improve thephysical properties of a polyphenylene ether polyamide blend such asimpact strength, and processability. The rubbery high-molecular weightmaterials include natural and synthetic polymeric materials showingelasticity at room temperature. More specifically, the rubbery highmolecular weight materials include natural rubber, thermoplasticelastomers as well as homopolymers and copolymers, including random,block and graft copolymers derived from various suitable monomers knownto those skilled in the art including butadiene, possibly in combinationwith vinyl aromatic compounds, especially styrene. As specific examplesof the rubbery high-molecular weight materials, there may be given, forexample, natural rubber, butadiene polymers, styrene copolymers,butadiene/styrene copolymers, isoprene polymers, chlorobutadienepolymers, butadiene/acrylonitrile copolymers, isobutylene polymers,isobutylene/butadiene copolymers, isobutylene/isoprene copolymers,acrylic ester polymers, ethylene propylene copolymers,ethylene/propylene/diene copolymers, thiokol rubber, polysulfide rubber,polyurethane rubber, polyether rubber (e.g. polypropylene oxide) andepichlorohydric rubber.

A preferred class of rubber materials are copolymers, including random,block and graft copolymers of vinyl aromatic compounds an conjugateddienes. Exemplary of these materials there may be given hydrogenated ornon-hydrogenated block copolymers of the A-B-A and A-B type wherein A ispolystyrene and B is an elastomeric diene, e.g. polybutadiene, radialteleblock copolymer of styrene and a conjugated diene, acrylic resinmodified styrene-butadiene resins and the like; and graft copolymersobtained by graft-copolymerization of a monomer or monomer mixcontaining a styrenic compound as the main component to a rubber-likepolymer. The rubber-like polymer used in the graft copolymer as alreadydescribed herein includes polybutadiene, styrene-butadiene copolymer,acrylonitrile-butadiene copolymer, ethylene-propylene copolymer,polyacrylate and the like. The styrenic compounds include styrene,methylstyrene, dimethylstyrene, isopropylstyrene, alpha-methylstyrene,ethylvinyltoluene and the like. The monomer which may be used togetherwith the styrenic compound includes, for example, acrylate,methyacrylate, acrylonitrile, methyacrylonitrile, methyacrylic acid,acrylic acid and the like.

Finally, additional thermoplastic elastomers suitable for use as therubbery material include thermoplastic polyester elastomers,thermoplastic polyether-ester elastomers, ethylenic ionomer resins andthe like.

The amount of the rubbery polymer used will be up to about 100 parts byweight, preferably from about 5 to about 50 parts by weight based on 100parts by weight of a mixture of polyphenylene ether and polyamide.However, when the amount is less than 2 parts by weight, the effect ofthe rubbery polymer to improve impact resistance is poor. When theamount is more than 100 parts by weight, the impact resistance is muchimproved, however, some loss of other physical properties may result. Inthe interest of balancing impact resistance and other physicalproperties, it is preferred to use less than 100 parts by weight of therubber polymer.

The polyphenylene ether-polyamide compositions may also comprise similaramounts, as referred to above, of alkenyl aromatic compounds. Thesealkenyl aromatic compounds may or may not be partially or whollycopolymerized with and/or grafted to the polyphenylene ether.Especially, suitable are the styrene resins described in for exampleU.S. Pat. No. 3,383,435, incorporated herein by reference. In general,the styrene resins will have at least 25% by weight of the polymer unitsderived from a vinyl aromatic compound of the formula: ##STR16## whereinR^(V) is hydrogen, (lower) alkyl or halogen, W is vinyl, halogen or(lower) alkyl, and p is 0 or an integer of from 1 to the number ofreplaceable hydrogen atoms on the benzene nucleus. Herein, the term"(lower) alkyl" is intended to mean alkyl of from 1 to 6 carbon atoms.

The term "styrene resins" as used broadly throughout this disclosure andthe appended claims includes, by way of example, homopolymers such aspolystyrene, polychlorostyrene and polybromostyrene, as well aspolystyrenes, including high impact polystyrenes, which have beenmodified by a natural or synthetic rubber, e.g. polybutadiene,polyisoprene, butyl rubber, ethylene-propylene diene copolymers-(EPDMrubber), ethylene-propylene copolymers, natural rubbers, polysulfiderubbers, polyurethane rubbers, styrene-butadiene rubbers (SBR), and thelike: styrene containing copolymers such as styrene-acrylonitrilecopolymers (SAN), styrene-butadiene copolymers, styrene-bromostyrenecopolymers especially styrene-dibromostyrene copolymers,styrene-acrylonitrile-butadiene terpolymers (ABS),poly-alpha-methylstyrene, copolymers of ethylvinyl benzene anddivinylbenzene and the like.

Finally, in addition to the foregoing, the resin compositions of thepresent invention may further comprise other reinforcing additives,including glass fibers, carbon fibers, mineral fillers and the like aswell as various flame retardants, colorants, stabilizers and the likeknown to those skilled in the art.

The method for producing the resin compositions of the present inventionis not particularly limited, and the conventional methods aresatisfactorily employed. Generally, however, melt blending methods aredesirable. The time and temperature required for melt-blending are notparticularly limited, and they can properly be determined according tothe composition of the material. The temperature varies somewhat withthe blending ratio of the polyphenylene ether to polyamide, but it isgenerally within a range of 270° to 350° C. A prolonged time and/or ahigh shear rate is desirable for mixing, but the deterioration of theresin composition advances. Consequently, the time needs to bedetermined taking into account these points.

Any of the melt-blending methods may be used, if it can handle a moltenviscous mass. The method may be applied in either a batchwise form or acontinuous form. Specifically, extruders, Banbury mixers, rollers,kneaders, and the like may be exemplified.

All ingredients may directly be added to the processing system or onepolymer. With respect to the other ingredients of the composition, allingredients may be added directly to the processing system or certainadditives may be precompounded with each other or either polymer priorto blending with the other polymer. For example, the polyphenylene ethermay be precompounded with the rubber polymer and/or the compatibilizerand subsequently compounded with the polyamide.

All the aforementioned patents or applications are hereby incorporatedby reference. The following examples are given to illustrate theinvention without limitation.

Synthesis of Poly-(2,6-Dimethyl-1,4-Phenylene Ether

To a stainless steel reactor equipped with an agitator, oxygen spargepipe, and heat exchanger was added in order: 332 parts be weighttoluene, 10 parts 2,6-xylenol, 4.3 parts dimethyl-n-butylamine, 1.0parts di-n-butylamine, 0.3 parts di-t-butylethylenediamine, and asolution of 0.08 parts cuprous oxide dissolved in 0.8 parts of 50 weightpercent aqueous HBr. Oxygen is sparged into the agitated solution while90 parts of 2,6-xylenol is pumped into the reactor over a period of 40minutes. The reactor temperature is kept at about 35° C. during theportion of the reaction where the molecular weight is increasing. Afterabout 120 minutes the oxygen flow is stopped. The temperature of thepolymer solution is maintained at between 50° to 70° C. during whichtime the by-product 2,6-dimethyldiphenoquinone reacts with an isincorporated into the polymer. Nitrilotriacetic acid is added to thepolymer solution to complex with the copper catalyst and is removed witha liquid-liquid centrifuge. The copper free polymer solution at thispoint is referred to as "body feed" and contains 18 to 22 weight percentpolymer. The polymer solution is concentrated to about 30 weight percentsolution by distilling off solvent prior to precipitating the polymerwith methanol. The 30 percent polymer solution is called "pre con"solution. Dried, filtered polymer produced in this manner is in the formof polyphenylene ether powder. Such powder may be functionalized asdescribed in the following example or may be utilized as theconventional polyphenylene ether in a polyamide-polyphenylene ethercomposition. The polyphenylene ether polymer produced by this processhas an intrinsic viscosity of, approximately, 0.45 dl/g as measured inchloroform at 25° C.

EXAMPLE 1 Synthesis of Functionalized-Polyphenylene Ether

Various polyphenylene ether-trimellitic anhydride acid chloride reactionproducts were prepared. In one method, a 30% by weight solution ofpoly(2,6 dimethyl-1,4-phenylene) ether in toluene (obtained directlyfrom the polymerization of 2,6-xylenol in toluene after removal ofcopper catalyst) was utilized ("PRE CON" PPE). In another method, an"isolated PPE" obtained by methanol precipitation and dissolved in 500parts toluene was used. In either case, one hundred parts of PPE wasreacted with between 1.7 to 2.3 parts of trimellitic anhydride acidchloride (TAAC), and between 4.1 to 5.8 parts of dimethyl-n-butylamine(DMBA) was utilized as an acid acceptor. The reactions were carried outat 95° C. for between 0.5 to 3.0 hours.

The TAAC was obtained from Aldrich Chemical at a purity of 99%,molecular weight 210.57 g/mole, and melting point of 66° to 68° C.

The reaction products were purified by precipitation in methanol andthereafter dried overnight in a vacuum oven at 60° to 80° C.

The formation of PPE-TAAC was verified by infrared analysis whichindicated a reduction of a known PPE hydroxyl peak at 2650 to 2900 nmand the appearance of a carbonyl absorption peak appeared at 1730-1740cm⁻¹.

Table 1 details conditions for reaction of PPE and TAAC.

                                      TABLE 1                                     __________________________________________________________________________    Conditions For Reaction of PPE With TAAC                                      WT % PPE      WEIGHT % PPE                                                                            g TAAC/                                                                             g DMBA/                                                                             TIME AT                                   SAMPLE DESCRIPTION                                                                          in TOLUENE                                                                              100 g PPE                                                                           100 g PPE                                                                           95° C. hrs.                        __________________________________________________________________________    Methanol Ppt. PPE                                                                           20        2.1   4.1   3                                         Methanol Ppt. PPE                                                                           20        2.3   4.1   1.5                                       Pre Con PPE   30        2.3   5.8   1.5                                       Pre Con PPE   30        2.3   5.8   0.5                                       Pre Con PPE   30        1.7   5.8   0.5                                       __________________________________________________________________________

EXAMPLES 2-3 Compatibilization of Polyphenylene Ether-Polyamide Blends

PPE-TAAC prepared as described above was evaluated as a compatibilizerfor PPE-polyamide blends and its performance was compared with a knowncompatibilizing agent, maleic anhydride, in a variety of blends.

The maleic anhydride was obtained from Aldrich at 99% purity, molecularweight 98.06 g/mole, and melting point of 54°-56° C. The polyamide was ageneral purpose nylon (6/6), Zytel-101, obtained from DuPont. The PPEwas poly(2,6 dimethyl-1,4-phenylene) ether resin manufactured by GeneralElectric Company in the manner described above.

Samples were extruded using a 28 mm Werner-Pleiderer twin screw extruderat 65% torque and full RPM with a heat profile of 350°, 450°-500°, 550°,550°, 550°, and 550° F.

Samples were molded on a 3 oz. Newbury injection molding machine at550°/150° C., 15/40 sec cycle, 100 RPM and 100 PSI back pressure.

Specimens used for HDT, Izod impact, and tensile tests were 1/8 inch×1/2inch×21/2 inch minibars. Dynatup falling dart impact test specimens were1/8 inch×4 inch round discs.

Table 2 demonstrates improvements in compositions of the presentinvention in comparison with non-compatibilized blends or thosecompatibilized with maleic anhydride. Note that degree of chemicalresistance can be judged by the retention of tensile yield strength forspecimens in a testing environment of 185° F. for three days in Fordbrake fluid.

                  TABLE 2                                                         ______________________________________                                                       COMPATIBILIZED                                                                PPE/POLYAMIDE BLENDS                                           SAMPLE           A*     B*     C*    2    3                                   ______________________________________                                        PPE              49     49     49    24.5 --                                  PPE-TAAC         --     --     --    24.5 49                                  NYLON 6,6        41     41     41    41   41                                  MALEIC ANHYDRIDE --     .50    1.0   --   --                                  KG-1651**        10     10     10    10   10                                  HDT ('F) @ 264 psi                                                                             367    368    380   357  360                                 IZOD (ft. lb/in) .10    3.5    3.3   5.9  4.6                                 DYNATUP (in. lb) 2      363    334   387  312                                 TENSILE YIELD (kpsi)                                                                           7.3    8.6    8.5   9.0  9.1                                 TENSILE STRENGTH (kpsi)                                                                        7.1    7.9    8.0   8.3  8.0                                 TENSILE ELONGATION %                                                                           11     123    124   140  89                                  SHRINK (in/in × 10.sup.-3)                                                               14.4   10.6   9.8   10.2 9.3                                 T.Y. ORIGINAL    7.3    8.6    8.5   9.0  9.1                                 (NO AGEING)                                                                   0% STRAIN                                                                     % ORIGINAL T.Y.  96     101    100   99   100                                 1/2% STRAIN                                                                   % ORIGINAL T.Y.  90     101    102   98   101                                 1% STRAIN                                                                     % ORIGINAL T.Y.  79     99     99    99   99                                  2% STRAIN                                                                     % ORIGINAL T.Y.  44     57     87    97   80                                  ______________________________________                                         *Comparative                                                                  **Kraton Rubber, Shell Chemical Co. (styreneethylene-butylene-styrene         copolymer)                                                               

EXAMPLES 4-7

The compositions described in Table 3 demonstrate the significantimprovements in physical properties exhibited by blends of the presentinvention. Especially notable are improvements in impact strength.

                                      TABLE 3                                     __________________________________________________________________________                    Additional PPE/Polyamide Blends                               SAMPLE          4   5   D*  E*  6   7                                         __________________________________________________________________________    PPO             24.5                                                                              24.5                                                                              50  25  25  12.5                                      PPO-TAAC (isolated)                                                                           24.5                                                                              --  --  --  --  --                                        PPO-TAAC (body feed)                                                                          --  24.5                                                                              --  --  25  12.5                                      NYLON 6,6       41  41  50  75  50  75                                        KG-1651         10  10  10  10  10  10                                        HDT ('F) @ 264 psi                                                                            361 370 374 373 372 371                                       IZOD (ft. lb/in)                                                                              5.4 7.2 0.3 0.9 4.9 3.7                                       DYNATUP (in. lb)                                                                              366 341 13  141 420 427                                       TENSILE YIELD (kpsi)                                                                          8.9 9.1 8.3 8.7 9.2 9.1                                       TENSILE STRENGTH (kpsi)                                                                       8.0 8.0 8.1 8.1 8.1 7.9                                       TENSILE ELONGATION (%)                                                                        98  80  16  56  72  86                                        SHRINK (in/in × 10.sup.-3)                                                              8.0 7.9 9.5 9.8 7.7 7.9                                       FLEXURAL MODULUS                                                                              --  --  318 325 322 337                                       FLEXURAL STRENGTH                                                                             --  --  12.7                                                                              12.8                                                                              13.1                                                                              13.7                                      (kpsi)                                                                        DELAMINATION    None                                                                              None                                                                              None                                                                              None                                                                              None                                                                              None                                      T.Y. ORIGINAL   8.9 9.1 8.3 8.7 9.2 9.1                                       (NO AGEING)                                                                   __________________________________________________________________________     *Comparative Examples                                                    

EXAMPLES 8-12

The solubility of PPE-Polyamide blends in formic acid and toluene wasevaluated. Table 4 demonstrates that compositions of the presentinvention exhibit considerably more reaction of PPE with Nylon 6,6 whenPPE-TAAC is used as a compatibilizer than when maleic anhydride is usedas a compatibilizer as evidenced by the decreasing solubility of theformic acid insoluble fraction of the blends in toluene.

                                      TABLE 4                                     __________________________________________________________________________                 Solubility of PPE/Polyamide Blends                               SAMPLE       F* G* H* I* J* 8  9  10 11 12                                    __________________________________________________________________________    PPE          50 50 50 50 50 47.5                                                                             45 40 25 --                                    PPE-TAAC     -- -- -- -- -- 2.5                                                                              5  10 25 50                                    Maleic Anhydride                                                                           -- .25                                                                              .5 1.0                                                                              2.0                                                                              -- -- -- -- --                                    NYLON 6,6    50 50 50 50 50 50 50 50 50 50                                    % Soluble in 90% Formic                                                                    50.5                                                                             50.3                                                                             50.4                                                                             48.4                                                                             50.4                                                                             50.3                                                                             50.7                                                                             50.6                                                                             49.1                                                                             48.6                                  Acid (25 C)                                                                   % Soluble in Toluene                                                                       93.1                                                                             83.8                                                                             83.7                                                                             87.2                                                                             88.3                                                                             88.1                                                                             81.5                                                                             77.8                                                                             59.7                                                                             25.3                                  (of formic acid insoluble                                                     material 25 C)                                                                __________________________________________________________________________     *Comparative Examples                                                    

EXAMPLES 13-17

Table 5 demonstrates the effect of various levels of compatibilizers inPPE-Polyamide blends. Compatible PPE-Polyamide blends of the presentinvention can be provided with a range of suitable properties asrequired for varied applications.

                                      TABLE 5                                     __________________________________________________________________________                    Effect of Various Levels of Compatibilizers                   Sample          K* L* M* N* O* 13 14 15 16 17 P* Q* R*                        __________________________________________________________________________    PPE             50 50 50 50 50 47.5                                                                             45 40 25 -- 100                                                                              -- --                        PPE-TAAC        -- -- -- -- -- 2.5                                                                              7  10 25 50 -- -- --                        NYLON 6,6**     50 50 50 50 50 50 50 50 50 50 -- 100                                                                              100                       MALEIC ANHYDRIDE                                                                              -- .25                                                                              .50                                                                              1.0                                                                              2.0                                                                              -- -- -- -- -- -- -- --                        HDT ('F) @ 264 psi                                                                            416                                                                              382                                                                              386                                                                              381                                                                              384                                                                              377                                                                              392                                                                              387                                                                              373                                                                              376                                                                              384                                                                              388                                                                              394                       IZOD (ft. lb/in)                                                                              .16                                                                              .24                                                                              .16                                                                              .24                                                                              .44                                                                              .12                                                                              .16                                                                              .12                                                                              .32                                                                              .40                                                                              .80                                                                              .36                                                                              1.04                      DYNATUP (in. lb)                                                                              5  16 35 33 20 7  9  10 15 24 21 17 314                       TENSILE YIELD (kpsi)                                                                          10.1                                                                             11.3                                                                             10.8                                                                             11.4                                                                             11.5                                                                             10.7                                                                             11.4                                                                             11.5                                                                             11.3                                                                             11.3                                                                             11.8                                                                             12.5                                                                             12.6                      TENSILE STRENGTH (kpsi)                                                                       9.2                                                                              6.9                                                                              7.4                                                                              6.9                                                                              7.3                                                                              10.6                                                                             11.3                                                                             7.0                                                                              6.7                                                                              6.9                                                                              9.8                                                                              4.8                                                                              8.4                       TENSILE ELONGATION (%)                                                                        11 52 142                                                                              105                                                                              73 17 19 49 66 73 76 63 200                       SHRINK (in/in × 10.sup.-3)                                                              9.2                                                                              8.1                                                                              8.2                                                                              7.5                                                                              7.6                                                                              8.5                                                                              7.6                                                                              6.6                                                                              6.4                                                                              6.5                                                                              5.3                                                                              19.8                                                                             18.4                      T.Y. ORIGINAL   10.1                                                                             11.3                                                                             10.8                                                                             11.4                                                                             11.5                                                                             10.7                                                                             11.4                                                                             11.5                                                                             11.3                                                                             11.3                                                                             11.8                                                                             12.5                                                                             12.6                      (NO AGEING)                                                                   0% STRAIN                                                                     % ORIGINAL T.Y. 93 99 105                                                                              100                                                                              99 107                                                                              97 99 101                                                                              97 76 94 94                        1/2% STRAIN                                                                   % ORIGINAL T.Y. 96 101                                                                              107                                                                              100                                                                              100                                                                              107                                                                              86 99 102                                                                              103                                                                              0  95 95                        1% STRAIN                                                                     % ORIGINAL T.Y. 105                                                                              100                                                                              107                                                                              101                                                                              101                                                                              106                                                                              100                                                                              99 102                                                                              102                                                                              0  94 96                        2% STRAIN                                                                     % ORIGINAL T.Y. 80 81 105                                                                              99 98 105                                                                              77 98 100                                                                              99 0  94 94                        __________________________________________________________________________     *Comparative Examples                                                         **Nylon 6.6 in example Q has been extruded once following the same            extrusion condition used for preparation of PPE/Nylon 6.6 blends before       molding. Nylon 6.6 in example R is the virgin resin.                     

EXAMPLES 18-25

The following examples demonstrate the utility of providing compatibleblends of polyphenylene ether and a variety of polaymdes includingpolyamide 6/6, polamide 6, polyamide 12, and polyamide 4/6. In theseexamples, the PPE is poly(2,6-dimethyl-1,4-phenylene)ether resin havingan intrinsic viscosity of, approximately, 0.45 dl/g as measured inchloroform at 25° C. The SEBS rubber is Shell Kraton G 1651styrene-ethylene-butylene-styrene copolymer. The sources of polyamideare noted in the tables. All parts are by weight.

                  TABLE 6                                                         ______________________________________                                                       Polyphenylene                                                                 Ether-Polyamide 6/6 Blends                                                    5*    18      T*     19                                        ______________________________________                                        Composition                                                                   PPE              50      25      45   22.5                                    Polyamide 6/6**  50      50      45   45                                      PPE-TAAC         --      25      --   22.5                                    SEBS Rubber      --      --      10   10                                      Properties                                                                    Unnotched Izod (ft-lbs./in)                                                                    3.6     9.1     19.9 no break                                Notched Izod     0.2     0.4     0.6  3.1                                     Tensile Yield at Break (KPSI)                                                                  8.6     9.8     8.2  7.8                                     Elongation (%)   2.3     3.2     5.4  30.2                                    HDT (°F., 66 PSI)                                                                       >400    >400    390  387                                     ______________________________________                                         *Comparison                                                                   **DuPont Zytel 101 Polyamide 6/6                                         

                  TABLE 7                                                         ______________________________________                                                        Polyphenylene                                                                 Ether-Polyamide 6/6 Blends                                                    U*   20      V*     21                                        ______________________________________                                        Composition                                                                   PPE               50     25      45   22.5                                    Polyamide**       50     50      45   45                                      PPE-TAAC          --     25      --   22.5                                    SEBS Rubber       --     --      10   10                                      Properties                                                                    Unnotched Izod (ft-lbs./in)                                                                     4.2    5.1     9.3  no break                                Notched Izod      --     --      0.3  2.7                                     Tensile Yield at Break (KPSI)                                                                   8.5    8.4     7.9  7.1                                     Elongation (%)    3.1    3.0     4.3  19.8                                    HDT (°F., 66 PSI)                                                                        371    356     363  354                                     (±5° F.)                                                            ______________________________________                                         *Comparison                                                                   **NYCOA 471 Polyamide 6, Nylon Company of America                        

                  TABLE 8                                                         ______________________________________                                                        Polyphenylene                                                                 Ether-Polyamide 12 Blends                                                     W*   22      X*     23                                        ______________________________________                                        Composition                                                                   PPE               50     25      45   22.5                                    Polyamide**       50     50      45   45                                      PPE-TAAC          --     25      --   22.5                                    SEBS Rubber       --     --      10   10                                      Properties                                                                    Unnotched Izod (ft-lbs./in)                                                                     4.6    11.3    3.9  no break                                Notched Izod      0.3    0.8     0.3  3.1                                     Tensile Yield at Break (KPSI)                                                                   6.7    7.0     6.3  5.6                                     Elongation (%)    3.0    10.4    4.1  23.3                                    HDT (°F., 66 PSI)                                                                        319    303     325  297                                     (±5° F.)                                                            ______________________________________                                         *Comparison                                                                   **Huels L1901 Polyamide 12                                               

                  TABLE 9                                                         ______________________________________                                                        Polyphenylene                                                                 Ether-Polyamide 4/6 Blends                                                    Y*   24      Z*     25                                        ______________________________________                                        Composition                                                                   PPE               50     25      45   22.5                                    Polyamide**       50     50      45   45                                      PPE-TAAC          --     25      --   22.5                                    SEBS Rubber       --     --      10   10                                      Properties                                                                    Unnotched Izod (ft-lbs./in)                                                                     6.6    34.3    4.7  no break                                Notched Izod      0.5    0.7     0.6  4.2                                     Tensile Yield at Break (KPSI)                                                                   9.4    10.8    8.1  8.9                                     Elongation (%)    3.4    10.9    3.7  31.6                                    HDT (°F., 66 PSI)                                                                        414    406     402  399                                     (±5° F.)                                                            ______________________________________                                         *Comparison                                                                   **DSM Polyamide 4/6                                                      

We claim:
 1. A functionalized-polyphenylene ether compound comprised ofthe reaction product of a polyphenylene ether polymer and a compoundhaving the general formula (i)-Z-(ii) that contains both group (i) whichis at least one polyphenylene ether-philic acylfunctionalized moiety;and group (ii) which is at least one polyamide-philic moiety; andwherein Z is a divalent hydrocarbon radical linking groups (i) and (ii),provided that groups (i) and (ii) are not both the simultaneouslycarboxylic acid groups.
 2. A composition as in claim 1 wherein saidpolyphenylene ether polymer is selected from the groups consisting ofpoly(2,6-dimethyl-1,4-phenylene) ether and copolymers of(2,6-dimethyl-1,4-phenylene) and (2,3,6-trimethyl-1,4-phenylene) ethers.3. A composition as in claim 1 wherein the compound of the formula(i)-Z-(ii) contains a group (i) moiety of the formula ##STR17## where Xis F, Cl, Br, I, OH, OR, or ##STR18## wherein R is H, an alkyl radicalor an aryl radical.
 4. A composition as in claim 1 having a compound ofthe formula (i)-Z-(ii) wherein group (ii) is at least one moietyselected from the group consisting of carboxylic acid, acid anhydride,acid amide, imido, carboxylic acid ester, amino or hydroxyl groups.